Complexes of dissimilar metals and methods of making same



United States Patent COMPLEXES OF DISSHVIILAR METALS AND 1 METHODS OFMAKING SAME Peter A. (Assetr, Cleveland, Thomas W. Mastin, Willoughby,and Alan Rhodes, Euclid, Ohio, assiguors to The Lubrizol Corporation,Wicklitfe, Ohio, a corporation of Ohio 1 No Drawing. ApplicationNovember 3, 1952,

1 Serial No. 318,525

Claims. (Cl. 260-504) This invention relates to new compositions ofmatter, and more particularly pertains to novel organic salt complexesand novel methods of producing same.

It is now well known that when preparing a salt or soap of an organicacid, the mere use of an excess of neutralizing agent, which in theprior art has been in the form of an oxide, hydroxide, carbonate, etc.of a desired metal, results in a product which contains an amount ofmetal in excess of that theoretically required to replace the acidichydrogens of the organic acid used as a starting material.

An object of the present invention is to provide novel salt complexes.Another object of the present invention is to provide new methods ofproducing novel salt complexes. A further object of the presentinvention is to provide novel salt complexes which are especiallyadapted for use in lubricants. Other objects or advantages of thisinvention will be apparent from the following explanation anddescription thereof.

Essentially the present invention comprises novel salt complexes formedwith an oil-soluble acidic organic compound and/or the salt thereof;'amaterial which is hereinafter referred to as the promoter; salts orbases; and

water.

More particularly, the present invention is concerned with saltcomplexes which are prepared by the method (1) compounds having theformula AH, in

which A is an anionic radical and H is hydrogen, which compounds:

(a) are water-soluble at a temperature of 50 C. to the extent of atleast 0.0005 and (b) in the presence of water, have an ionizationconstant greater than about 1 X 10- at about 25 C. and the saturatedaqueous solutions of which at about 25 C. have pH values no greater than7.0;

and which compounds are selected from the class consisting of:

(11') organic compounds (b) inorganic compounds containing a pluralityof atoms of an acid forming ele- 'ment; (2) the salts of the compoundsdefined by (1) above; the relative amounts of (i) and (ii) usedbeing inthe range of from about one 2,767,209 Patented Oct. 16, 1956 equivalentof (i) to about ten equivalents of (ii) to about ten equivalents of (i)to about one equivalent of (ii); (iii) compounds other than thoseselected as components (i) .and (ii) selected from the class consistingof:

(1) salts; and (2) bases;

in an amount such that there are present in the mass a total ofsubstantially more than one equivalent of cationic salt-formingradicals, including those present in components (i) and (ii), perequivalent of (i) plus (ii); and

(iv) materials selected from the class consisting of:

(1) water;

(2) the water-soluble alcohols and mixtures of such alcohols, and

(3) mixtures of water and such alcohols in an amount, inclusive of thatin chemical combination with all of the components present, equal to atleast one mole per mole of (ii);

II. and then maintaining the mass at a temperature and for a period oftime sufficient to drive off substantially any free water and alcohol,including water and alcohol of hydration, which may be present.

Optionally, the above salt complex can be further modi fied by:

' III. Treating the mass with suflicient amounts of a material which inthe presence of the mass will form a material having a higher ionizationconstant than AH, to liberate in the form of AH, a substantial portionof the radical A originally present in (ii).

If desired, the above salt complexes prepared in accordance with StepIII can then undergo treatment to remove from the mass so much of AH asmay have been formed by Step III.

As described above, the inorganic promoter is a compound containing aplurality of atoms of an acid forming element. However, it should beunderstood for the purposes of this invention that the above descriptionof the inorganic promoter includes those compounds con-- taining aplurality of atoms of an element capable of forming acids either incombination with hydrogen alone or in combination with hydrogen andoxygen. Further, for the present invention those inorganic promoterswhich contain a non-metallic acid forming element are preferred.

This application is a continuation-in-part of our copending application,Serial No. 216,101, filed March 16, 1951 and is a continuation-in-partalso of our related copending applications, Serial No. 216,102 now U. S.Patent 2,617,049; Serial No. 216,103 now U. S. Patent 2,616,924; SerialNo. 224,458 now U. S. Patent 2,695,910;

Serial No. 263,961 now U. S. Patent 2,616,925; Serial No. 263,962 now U.S. Patent 2,616,911; Serial No. 263,963 now U. S. Patent 2,616,904;Serial No. 276,461 now abandoned; and Serial No. 276,462 now U. S.Patent 2,616,905.

In our aforesaid parent application Serial No. 216,101 there isdisclosed the process of producing certain novel organic salt complexesand the novel products resulting from such processes. The presentinvention is an extension of the teaching of said parent case in that ithas now been discovered that the processes disclosed in said parentapplication may be utilized in producing novel complexes which haveunexpectedly good characteristics and which complexes are characterizedby the inclusion therein of a plurality of diflferent metals.

The utilization of a plurality of different metals leads to advantagesnot only in the production of products .which have properties whichcannot be achieved by the use of a single metal and also makes possiblethe production of complexes in certain respects like those produced bythe process of said parent case at considerable savings and costs. Thelatter is especially true when the organic portion of the complex isderived from those organic sulphonic acids which are produced byprocesses which yield the sulphonic acid in the form of the sodium salt.

Examples of such processes of producing sulphonic acids and in which thelatter is recovered in the form of its sodium salt are those processesnow commonly employed for the production of mahogany sulphonic acids aswell as the other sulphonic acids derived from mineral oil fractionsincluding the process of treating a mineral oil fraction with chlorineand 802. Another class of sulphonic acids which are usually producedinitially as the sodium salt are the alkylated aromatic snlphonic acidsparticularly the dodecyl benzene sulphonic acids.

In the prior art processes for producing polyvalent metal salts orpolyvalent metal complexes of sulphonic acids which utilizes as astarting material the sodium salt as above defined, it has been commonpractice to begin with such sodium salt and then by the well-knownprocess of double decomposition and by using a chloride of the desiredmetal, the sodium of such salt is replaced by the metal of saidchloride. This procedure has generally been followed in the productionof materials useful as detergents in lubricating oils since the saltscontaining only an alkali metal such as sodium, as the metal have notbeen found to be particularly effective, at least not nearly aseffective as similar salts in which the metal is a polyvalent metal suchas berium, for example.

In accordance with our present invention it has been found that when anormal salt such as a sulphonate of a metal which is not particularlyeffective as a lubricating oil detergent is complexed with another metaland particularly with a metal whose normal salts are outstandinglysuperior, a resultant complex is produced which has satisfactoryproperties while at the same time costing much less to produce. Thus,for example, it has been found that the normal sodium salt of any of thesulphonic acids mentioned above may be directly complexed with anotherbasically reacting compound so as to eliminate not only the expensivedouble decomposition step, but at the same time utilizing as a part ofthe metal content of the final complex a metal which is less expensivethan those which are found to give best results when used alone.

A mixture of different normal salts may be used as the startingmaterial. These normal salts may differ both as to their anion andcation substituents. Thus, when utilizing the same anions and differentcations, the end product will contain such different cations. In thisconnection it has been found that unexpectedly good results can besecured when using different anions when different cations are employedin the starting material, or more accurately in the formation of thenormal salt component of the complex. With regard to the normal saltswhich may thus be employed in preparing the complexes of the presentinvention, it will be noted that they include the following: (a) asingle starting acid neutralized with a single metal; (b) differentportions of a single starting acid neutralized with different metals;different starting acids neutralized with the same metal; and (d)different starting acids neutralized with different metals.

Similarly by the use of a plurality of different basically reactingmaterials which differ from each other as to the metal present, aplurality of different metals can be supplied to the ultimate complex.Here again it will be found that for certain combinations of differentbasically react ing materials one or more of those used may be in theform of the oxide, whereas at least one of those concurrently used maybe in the form of the hydroxide.

With regard to the possible third source of metal i. e. as a substituentof the promoter it has been found that a plurality of different metalsmay be introduced through 4 1 this reagent. Thus, for example, whenusing any promoter salt such as a phenate the entire'mass ofpromot'et'may contain a plurality of different cations.

THE OIL SOLUBLE ACIDIC ORGANIC COM- POUNDS AND/ OR THE SALTS THEREOF Theoil-soluble acidic organic compounds and/ or the salts thereof employedfor the purposes of the present invention include a variety of classesof compounds, such a as the aliphatic or aromatic organic acids e. g.,the sulfur acids, the carboxylic acids, acids of phosphorus, etc., orthe salts of such acids, including the corresponding thio acids of anyof the foregoing as well as mixtures of the same. The aromatic compoundsinclude the monoor polynuclear types of the benzenoid and heterocyclicclasses; whereas the aliphatic compounds are for example the acyclic andcycloaliphatic compounds. It is intended that all such compounds be oilsoluble for this invention, and in the preferred instance oil solubilityis meant that the salt of the acidic organic compound will possess asolubility of at least about 10% in Pennsylvania conventionally refinedmineral oil having a viscosity of about 150 SUS at F., or what iscommonly known as Pennsylvania neutral oil.

Specific illustration of the types of oil-soluble acidic organiccompounds or the salts thereof which can be employed in the process ofthis invention may be found in copending application, Serial No. 216,101at page 10. line 22 through page 22, line 23.

It has been found that metal complexes of considerable utility may beproduced when using as the starting material a mixture of at least twodifferent sulfonic acid compounds.

Highly useful in this respect are mixtures containing (a) at least onepetroleum derived sulfonic acid com pound, and (b) at least onealkyl-aromatic sulfonic acid compound. Particularly preferred aremixtures of mahogany sulfonic acids or salts with alkyl-benzene sulfonicacids or salts. The ratio of equivalents of all; is preferably between0.1 and 10.

The following examples illustrate a number of specific combinations ofdifferent sulfonic acid compounds which may be used as startingmaterials for the production of our metal complexes. In each instance,the corresponding salts of the s'ulfonic acids are also contemplated.

Mixture chemical No. Components equivalums 1 {mahogany sull'onlc acid 1.0 di-isododeey] benzene suite 1.0 white oil sulfonic acid. 1.0 2mahogany sulfoulc acid 1.0 dl-isodocecyl benzene suitor-lea d. 25.0 3white oil sulionic acid 1. 0 di-isododeeyl benzene sulioni d. '3. 0 4 v{mahogany sultonic acid 10. wax-substituted phenol snlfonic acid. 1. 0 5mahogany sulionie acid 5. i1 wax-substituted naphthalene 1.0 6mahoganysulfonicacid..... 1.0 wax-substituted benzene sulfonic acid. 9.(i 7 {petrolatum sulionie acid 1. 0 white oil sulfonic acid. 2.0 8{mahogany sulfonic acid 1. 0 petrolatum sullonic acid 1.0 9 {mahoganysulfonic acid i. 0 white oil sulfonic acid. 1.11 10 {polybuteue sultonicaeid 1. U mahogany sultonic acid" 5.0 n (was sultonic acid 0 mahoganysulionic acid... 2.0 12 icosyidiphenyiether sultonic cid 1.1)mahoganysulionleacid....... 7.0 {tri-capryl diphenyl other sulfonicacid 1. 0 mahogany sulfonic acid 2.5 H {bis-(diisobutyD-phcnolsulionicacid, .0 white oilsultonieocid 3." 15 {cetyl-chlorobenzeuc sullonieacid. 1. U mahogany snlfonic acid. 8. 16 {di-cetyl naphthalene snlionic10.0 mahogany sulfonic acid.... 1.0 mahogany sullonic acid 2. 0 17 whiteoil sulionic acid 1.0 di-lauryldiphcnyl other sulfonicncid -l-"di-isononyl benzene suliouic acid 1. 18 white oil disullonie acid 1.0di-lsooctadecyl benzene suli'onic acid.- 2.0

water soluble 15 C.

Mixture chemical No. Components equiv alents petroleum naphthenesulfonic acids 1. 19 mahogany sulfonic acid 1.0 polybutene-substltutedbenzene sulfomc acid- 1. 0 m {di-keryl benzene sulfonic acid 2. 0mahogany sulfonle acid 1.0 21 fuel oil substituted benzene sulfonicac 1. mabo any sulfonic acid 1.0 m steary naphthalene sulfonic acid 3. 0white oil sulfonic ac1d. 1. 0 wax-substituted phenothioxine sulfonicacid 1. O mahogany sulfonic acld 3. 5

THE PROMOTER The compound employed for the purposes hereunder can berepresented by the formula AH, in which A is an anionic radical and H ishydrogen and/or the salt thereof. The compounds AH have a watersolubility at a temperature of 50 C. to the extent of at least about0.0005% and will, in the presence of water at about 25 C., have anionization constant greater than about 1Xl0" as well as have a pH valuenot greater than 7 at about 25 C. when employed in saturated aqueoussolutions.

The promoter AH can be organic or inorganic. In the case of theinorganic promoter it is intended to include only those which contain aplurality of atoms of an acidforming element which are capable offorming acids either in combination with hydrogen alone or incombination with hydrogen and oxygen. It is preferred to use thosepromoters in which the acid-forming element is non-metallic.

With respect to the organic promoter AH, a particular subclass thereofincludes the compounds AXH in which A and H are defined as given above,and X is either oxygen or sulfur. More particularly, as for the organicpromoters, it is preferred to employ the salts of compounds AH whichhave oil solubility of less than 10% in a conventionally refined solventextracted Pennsylvania oil having a 150 SUS 100 F., commonly referred toas Pennsylvania 150 neutral oil.

Classes of promoters and specific examples thereof which may be used forthe purposes of this invention are disclosed in copending application,Serial No. 216,101 at page 23, line 18 through page 38, line 21.

- SALTS AND BASES (THE BASING MATERIAL) The'salt or base employedfurnishes the cationic saltforming radical to the desired salt complex.These salts or bases should preferably have a water solubility of atleast about 0.0003% to 50 C., and still more preferred are basiccompounds, i. e., those compounds which give an'alkaline reaction or pHvalue greater than 7 in aqueous solutions.

Specific examples of metal cations and anions which may be combined toform the salts and bases (basing materials) of this invention, as wellas specific examples of such salts and bases are disclosed in copendingapplication, Serial No. 216,101 at page 39, line 1 through page 47, line29.

The formation of the salt complex is accomplished with water or analcohol or mixtures of both. The water is present as a result ofaddition to the mixture, or is liberated from compounds incorporatedinto the mixture as a result of being subjected to processingtemperatures. It is preferred to employ water which is added to themixture.

The alcohol employed can be either monohydric or polyhydric, and shouldpreferably be at least about 5% Examples of monohydric alcohols aremethanol, ethanol, propanol-l, propanol-2, butanol-l, butanol-Z,isobutyl alcohol, t-butyl alcohol, pentanol-3, etc.; and examples ofpolyhydric alcohols are ethylene glycol, propylene glycol, butyleneglycol, amlylene glycol, hexylene glycol, pentaerythritol, etc.

Water and alcohol can be used together in effecting the formation of thesalt complex. Ordinarily mixtures of the same in any relative proportionare useful, however it is preferred to employ mixtures containing atleast 60% water.

THE ACIDIC MATERIAL As previously indicated, one form of the process ofthe present invention includes the step of treating the immediateproduct with an acidic material for the purpose of liberating therefromat least a portion of the material previously referred to as thepromoter. A particularly effective acidic material which has beenutilized for this purpose is carbon dioxide. We are aware of the factthat Modes in his Patent No. 2,501,731 suggested transforming a sodiumhydroxide-calcium sulphonate complex into the sodium carbonate-calciumsulphonate complex or the corresponding bicarbonate complex by blowingthe hydroxide complex with carbon dioxide at elevated temperatures. as;

In our process, the step of treating with an acidic material such ascarbon dioxide or even with air has the effect of liberating from theimmediate product formed a part at least of the anionic radical of thecompound used as the promoter material. Thus the presence in theimmediate product of the promoter material, in combined form, clearlydistinguishes the immediate product from any organic salt complex typematerial heretofore produced. Moreover, the nature of the product formedby regenerating from the immediate product at least a portion of theanionic radical of the promoter material leaves that product with acomposition which is quite different from prior art organic complexes.It is recognized that in accordance with the present invention, the saltform of promoter can be employed in forming the salt complex. However,notwithstanding this fact, upon treating the salt complex with theacidic material to be more particularly defined below, this saltcompound is released or liberated from association in the salt complexas the ionizable compound and not the salt.

The acidic material employed for this purpose can be either a liquid,gas, or solid just so long as the material when present in the masscontaining the salt complex will possess an ionization constant greaterthan the promoter which is released or liberated from association in thesalt complex. Thus, for the purpose of this specification and theappended claims, it is to be undertood that the acidic material includesa liquid, gas, or solid prior to being incorporated in the mass whichcontains the salt complex.

In the present invention, the acidic material usually employed is anacid or a gas. The acids can include the strong or weak types, such as,for example, hydrochloric, sulphuric,-nitric, carbonic, acetic acids,etc., whereas the gas is for the most part an anhydride or an acid or anacid anhydride gas.

The large number and variety of acidic materials can be best illustratedby the following specific examples, viz. HCl, S02, S03, CO2, air, N02,H23, N203, PCls, SOCl2, C102, H2Se, BFa, CS2, COS, etc.

From the above examples of compounds and classes of compounds which canbe used as acidic materials, it should be understood that all of themare not equivalent for this invention because under certain conditionssome are more desirable or effective than others.

Generally, the complex formed is prepared by heating the components, ata superatmospheric temperature while insuring thorough mixing and thenfurther heating -said mixture to substantially remove all free water oralcohol, including water and alcohol of hydration which may be present.which the complex can be formed, namely: (a) The compound AH or the saltthereof, is added to the oil-soluble salt of an acidic organic compound,followed by addition of an aqueous solution or suspension the salt orbase thereto. The mixture is held at a superatmospheric temperature fora reasonable length of time while insuringw The following methodsillustrate the manner by thorough: mixing, and then the total mixture isfurther heated tosubstantially remove all free water or alcoholincluding water or alcohol of hydration which maybe present; (5) Thesalt or base in a dry state is added to a mixture of oil-soluble acidicorganic compound or salt thereof, the compound AH or the salt thereofand either water, alcohol, or mixtures of alcohols or water andalcohol', heated to a superatmospheric temperature while insuringthorough mixing and then further heated to remove substantially all freewater or alcohol including water or alcohol of hydration which may bepresent; (c) The acidic organic compound is mixed with the compound AHor the salt thereof, then an aqueous solution or suspension or analcoholic solution or suspension of the salt or base is added thereto.The mixture is heated and agitated at a superatmospheric temperature fora time sufiicient to insure thorough mixing and followed by subjectingthe total mixture'to dehydration conditions in order to removesubstantially all free water or alcohol including water or alcohol ofhydration which may be present. ((1) A mixture of the oil-soluble acidicorganic compound or the salt thereof, the compound AH or the saltthereof, and the salt or base is heated and agitated at asuperatmospheric temperature for a time sufiicient to insure thoroughmixing, and followed by heating the total mixture in order to removesubstantially all free water or water of hydration which may be present;(e) The sediment when formed from any of the aforementioned methods canbe employed either alone or with an additional amount of compound AH orthe salt thereof in any of the three methods given above; (f)In any ofthe methods discussed herein for preparing a salt complex, a substantialincrease in cationic salt-forming radical content is effected bytreating the mass with an acidic material just after substantial amountsof water or alcohol or both, are driven off and just before the mass isfiltered.

In all of the methods described above for preparing the salt complex,the step of removing substantially all free water or alcohol includingwater or alcohol of hydration which may be present is accomplished at atemperature not substantially in excess of 350 C., preferably about 110to 200 C. The technique employed to remove the alcohol or waterincludes, for example, a conventional flash operation, heating undersubatmospheric, atmospheric, or superatmospheric pressures. It can,therefore, be seen that the temperature as well as the time foreffecting the substantial removal of the alcohol or water will generallyvary considerably depend on the technique employed therefor. Generally,the time required to effect substantial removal of water or alcohol whenemploying drying other than flash techniques is about 15 minutes orless, and can be as high as ll5 hours. Usually, however, atmosphericpressures will be employed for such an operation, and consequently itwill usually require about 1 to hours to remove substantially all wateror alcohol which may be persent. At a later stage of the process, theacidic material when used in gaseous form may be used to remove the lastportion of water.

For the purposes of this specification and the appended claims, therelative amounts of (l) the oil-soluble acidic organic compounds orsalts thereof, and (2) the prometer is expressed as the ratio ofequivalents of the former (1) to the latter (2). In accordancetherewith, the ratio of equivalents is from about 1 to to about 10 to 1,preferably from about 3 to 2 to about 7 to 2. The amount of salt or baseemployed in the process will be sufficient to have present in the totalmass at least more than about one euqivalent of cationic salt-formingradicals including those present in the oil-soluble acidic organiccompound or the salt thereof and the promoter per equivalent ofoil-soluble acidic organic compound or salt thereof plus the promoter.

The treatment of the salt complex with an acidic material is employedwhen it is desirable to lower the basic number of the salt complex and/or partially or substantially recover the promoter. a temperature ofabout 25 to 250 C., preferably about 120 to 170 C., and by employingabout 0.5 to 20% of acidic material based on the weight of salt complex.The time of treatment with the acidic material can vary considerablydepending on the desired result. As would be expected, short periods oftreatment might cause only partial liberation or release of the promoteror relatively small decreases in the basic number of the salt complex;however, in general, periods of treatment will range from about 0.25 to30 hours. In most cases, and particularly where it is desired to recoverthe promoter, the amount of acidic material used should be at leastequivalent to the amount of cationic salt forming radicals present asthe salt of the ionizable form of promoter. When it is desired toproduce a product having substantially neutral reaction, the amount ofacidic material used should be at least equivalent to the total cationicsalt forming radicals in excess of that present as the normal salt ofthe oil soluble organic acid.

In those instances where salts or bases containing metal are employed asthe basing agent the metal content of the complex will be defined as theratio of the total metal in the salt complex to the amount of metalwhich is in the form of a normal salt of the oil-soluble acidic organiccompound. In accordance therewith the present invention includes saltcomplexes containing metal ratios greater than l, and up to about 10 ormore. As for those complexes which are treated with an acidic materialit is to be noted that the metal ratio is substantially the same as inthe complex prior to treating. Consequently, for acidic material treatedcomplexes, the same metal ratios will apply as given above. Likewise,

when the salt complex is treated with an acidic material and thepromotor is removed from the resultant product by distillation orotherwise, it is found that the metal ratio will be substantially thesame as in the salt complex before treating with the acidic material.

It has been found that the salt complex can be prepared by using smallquantities of water, alcohol, or mixtures of both, such as about 1 moleof same per mole of salt or base which is employed as the basing agent.However, more usually about 5 to 50 moles of water, alcohol or mixturesof both per mole of salt or base used, and preferably about 15 to 30moles per mole.

To substantially increase the metal content of the salt complex, thetotal mass is treated with an acidic material just prior to filteringsame to separate the desired salt complex. This treatment is effected ata temperature of about 25 to 250 C. preferably about 120 to 170 C.,using about 0.5 to 20% of acidic material, based on the total mass, andfor a period of about 0.25 to 30 hours. Treatment with an acid anhydridegas may be accelerated by superatmospheric pressure.

In order to better understood the present invention, the followingspecific examples thereof are given; however it should be understoodthat no undue limitations or restrictions should be imposed by reasonthereof.

The following examples give the preparation of a plurality of productswhich range in cationic salt forming radical content from about that ofthe normal salt up I to many times that amount.

We have found that sulphate ash and/ or metal content values, and themetal ratio values calculated therefrom, are one of the most reliablemeans for characterizing certain of the salt complexes. As thedescription of the invention proceeds, it will become apparent that theneutralization number of a salt complex is in certain instances anunreliable index of the amount of excess cationic salt forming radicalsin such complex, since it is greatly affected by the type of basingagent employed and can be varied within wide limits withoutsignificantly changing the cationic salt forming radical content of theproduct by treatment of the mass with air, CO2, or the like.

This treatment is effected at The above is not to be construed as astatement that the neutralization number is not an important property ofa salt complex. For some uses, for example in lubrieants, it isadvantageous in certain instances to employ asalt complex of asubstantially neutral character, whereas in other instances a saltcomplex of high alkalinity has been found to produce the desiredresults.

The following example illustrates an attempt to incorrate astoichiometric excess of alkaline earth metal in an oil-soluble alkalimetal sulfonate without the use of a. promoter.

Example 1 To a mixture of 1330 grams (2.0 equivalents) of a 60% oilsolution of sodium petroleum sulfonate, 1048 grams of mineral oil, and250 grams of water there was added at 70 C. 217 grams (2.84 equivalents)of barium oxide, and the mixture was heated at reflux temperature fortwo hours. The water was removed in a period of five hours by heating to150 C. and holding at this temperature. The mixture was filtered througha siliceous filter aid. The filtrate showed the following analyses:

Basic No 15.5 Barium percent 2.3 Sodium do 2.7 Metal ratio 1.4

Basic No 62.1

Barium percent 8.45

Sodium do..-" 1.66

Metal ratio 2.99

Example 2 A mixture of 1285 grams (1.0 equivalent) of a 40% oil solutionof barium petroleum sulfonate (having a sulfate ash content of 10.0%),124 grams (0.6 equivalent) of diisobutyl phenol, 163 grams (3.9equivalents) of lithium hydroxide monohydrate and 200 grams of water washeated at 100 C. for one hour, then the temperature was raised slowly to150 C. and maintained there for an additional hour. The mixture wastreated with a stream of carbon dioxide at this temperature for onehour, dried at 150 C. for 30 minutes and filtered through a siliceousfilter aid. The oil-soluble, free-flowing filtrate was found to have thefollowing analyses:

Example 3 A mixture of 630 grams (1.0 equivalent) of petroleum sulfonicacid, 400 grams of mineral oil, 250 grams of water, and 54 grams (1.28equivalents) of lithium hydroxide was heated at reflux temperature forone hour. The mixture was cooled to 70 C., treated with 124 grams (0.6equivalent) of diisobutyl phenol and 302 grams (3.94 equivalents) ofbarium oxide, and heated at reflux temperature for one hour. Theresultant reaction mass then was dried by raising the temperature to 150C. and treated with a stream of carbon dioxide for an hour. Thiscarbonated product was dried further for 30 minutes at 150 C. andfiltered through a siliceous filter aid.

The oil-soluble, freeflowing filtrate was shown to have the followinganalyses:

Basic N 10.8 Barium percent..- 16.7 Lithium do 0.38 Metal ratio 4.56

Example 4 The potassium salt of a phosphorusand sulfur-containing acidwas prepared by treating a polybutene with phosphorus pentasulfide andsulfur and subsequently treating with steam. A mixture of 1080 grams(1.0 equivalent) of this salt, 205 grams of mineral oil, 124 grams (0.6equivalent) of diisobutyl phenol, 480 grams of water, and 302 grams(3.94 equivalents) of barium oxide was heated at reflux temperature forone hour, then freed of water by heating to 150 C. and maintaining thistemperature for one hour. A stream of carbon dioxide was bubbled intothe mixture for an hour and this temperature was maintained for anadditional 30 minutes. The mixture was filtered through a siliceousfilter aid, yielding an oil-soluble, free-flowing filtrate which wasshown to have the following analyses:

Basic No 1.18

Barium percent 12.9

Potassium do 2.2

Metal ratio 4.35

Example 5 A mixture of 1080 grams (1.0 equivalent) of the potassium saltof the phosphorusand sulfur-containing product prepared as in thepreceding example, 1285 grams (1.0 equivalent) of a 10.0% oil solutionof barium petroleum sulfonate, 248 grams (1.2 equivalents) of diisobutylphenol, 598 grams (7.8 equivalents) of barium oxide, 500 grams of water,and 400 grams of mineral oil was heated at reflux temperature for onehour, then freed of water by heating to 150 C. and maintaining thistemperature for one hour. The mixture was treated at this temperaturefor 2.5 hours with carbon dioxide, then heated at ISO-160 C. for anadditional 30 minutes. The carbon dioxide-treated mass was filteredthrough a siliceous filter aid, the oil-soluble, free-flowing filtratehaving the following analyses:

Example 6 A mixture of 998 grams (1.5 equivalents) of a 60% oil solutionof sodium petroleum sulfonate, 186 grams (0.9 equivalents) of diisobutylphenol, 717 grams of mineral oil, 300 grams of water, and 453 grams ofbarium oxide was heated at reflux temperature for one hour then freed ofwater by heating to 150 C. and holding at that temperature for anotherhour. Carbon dioxide was bubbled into the mixture at this temperaturefor two hours and heating was continued at 150160 C. for an additional30 minutes. The mixture was filtered through a siliceous filter aid,yielding an oil-soluble, free-flowing filtrate which was found to havethe following analyses:

tassium salt of the phosphorusand sulfur-containing acid prepared as inExample 4, 470 grams (0.42 equivalent) of a 40% oil solution of bariumpetroleum sulfonate (having 10.0% sulfate ash), grams of water, andgrams (0.51 equivalent) of diisobutyl phenol was Basic No 12.2

Barium percent 18.4

Potassium do 1.1

Metal ratio 5.1

Example 8 A mixture of 500 grams (0.42 equivalent) of the potassium saltof the phosphorusand sulfur-bearing acid prepared as described inExample 5, 470 grams (0.42

equivalent) of a 40% oil solution of barium petroleum sulfonatc (havinga sulfate ash content of 10.0%), 105 grams (0.51 equivalent) ofdiisobutyl phenol, and 100 grams of water was treated at 70 C. with 288grams (3.76 equivalents) of barium oxide, then heated at refiuxtemperature for an hour. The water was removed by heating to 150 C. Thistemperature was maintained for one hour prior to bubbling carbon dioxideinto the mixture for one hour, and for 30 minutes thereattcr.

The product was filtered through a siliceous filter aid. 1

The oil-soluble, free-flowing filtrate had the following analyses:

Basic No 14.1

Barium percent 16.7

Potassium do Metal ratio 4.5

Example 9 A mixture of 845 grams (1.0 equivalent) of lithium didodecylbenzene sulfonate, 53.5 grams (0.6 equivalent) of nitropropane, 302grams (3.94 equivalents) of barium oxide, 629 grams of mineral oil, and190 grams of water was heated at 100 C. for one hour, then thetemperature was raised slowly to 150 C. and maintained there for anadditional hour. The mixture was treated with a stream of carbon dioxideat this temperature for one hour, dried at 150-160" C. for 30 minutes,and filtered through a siliceous filter aid. The oil-soluble,free-flowingfiltrate was found to have the followinganalyses:

Basic No 0.42 Barium percent 13.7 Lithium do 0.24

Metal ratio 4.4

Example 10 Basic No 6.6 Barium percent 9.85 Sodium d 1.26 Metal ratio4.4

Example II A mixture of 630 grams (1.0 equivalent) of petroleum sulfonicacid, 878 grams of mineral oil, 310 grams of water, and 42 grams (1.0equivalent) of lithium hyi drox-ide monohydrate was heated at refluxtemperature for one hour. 70 C. and 36 grams (0.6 equivalents) of aceticacid and 302 grams (3.94 equivalents) of barium oxide were added. Thismixture was heated at reflux temperature for The lithium salt mixturewas cooled to one hour, then to 150 C., at which point carbon dioxidewas bubbled into the mixture for an hour. Heating was continued for anadditional minutes, then the mixture Example 12 A mixture of 500 grants(0.79 equivalent) of petroleum sulf-onic acid, 561 grams of mineral oil,120 grams of water, and grams (0.79 equivalent) of hydroxidemon-ohydrate was heated at reflux temperature for one hour. The lithiumsalt mixture was cooled to C. and 159.5 grams (0.48 equivalent) ofdi-n-hexyl dithiophosphoric acid and 240 grams (3.13 equivalents) ofbarium oxide were added. The resulting mixture was heated for one hourat reflux. temperature, then to 155 C. and treated for one hour withcarbon dioxide. Thereafter, the temperature of 150-160 C. was maintainedfor another hour and then the mixture was filtered through a siliceousfilter aid, the filtrate being an oilsoluble, slightly viscous liquidhaving the following analyses:

Basic No 53.8

Barium percent 14.7

Lithium dlo 0.11

Metal ratio 434 Example 13 Basic No. 29.2

Calcium percent 4.32

Lithium do 0.65

Metal ratio 5.14

Example 14 A mixture of 448 grams (1.66 equivalents) of sodiumnaphthenate, 223 grams (1.0 equivalent) of nonylphenol, 1620 grams ofmineral oil, and 500 grams of water was treated at 50 C. with 500 grams(3.27 equivalents) of barium oxide. This mixture then was heated 'atreflux temperature for one hour, and then was heated to 150 C. andtreated with carbon dioxide for minutes. The mixture was kept at -165 C.for an additional 30 minutes, then filtered through a siliceous filteraid. The filtrate was an oil-soluble, free-flowing liquid having thefollowing analyses:

Basic No 0.94 Barium .0 percent 8.9 Sodium do 1.15 Metal ratio 4.0

Approrrimatoly 800 grams of this material was heated an additional onehour at 150 C., then filtered through a siliceous filter nit], yieldingan oil-soluble, free-tlowing filtrate having the following analyses:

Basic No. 35.3 Sodium percent 0.37 Barium (l0 8.7 Metal ratio 2.4

13 Example 15 To a mixture of 630 grams (1.0 equivalent) of petroleumsulfonic acid, 824 grams of mineral oil, 66 grams (1.0 equivalent) ofpotassium hydroxide and 135 grams of water there was added at 50-60 C.124 grams (0.6 equivalent) of tetralin sulfonic acid and 203 grams (3.93equivalents) of strontium oxide. This mixture was heated at refluxtemperature for an hour, then dried by heating 150 C. A sample wasremoved and filtered, the filtrate showing the following analyses:

Basic No. 0.28 Potassium ...percent 2.2 Strontium do 2.76 Metal ratio2.32

The unfiltered product was treated further at 150-160" C. with carbondioxide for an hour, then filtered. The filtrate showed the followinganalyses:

Example 16 The strontium salt (1160 grams-1.0 equivalent) of white oilsulfonic acid was prepared by adding chlorosulfonated white oil toaqueous sodium hydroxide at 80-95 C. and treating the resulting sodiumsulfonate with strontium chloride at 90 C. The aqueous layer was removedand 1464 grams of mineral oil was added to the residue. The washed oillayer, strontium white oil sulfonate, was treated with 318 grams (1.0equivalent) of eetyl phenol and 275 grams (6.54 equivalents) of lithiumhydroxide monohydrate, and heated at reflux temperature for an hour,then heated up to 150 C. A sample of this material was dried further byheating at 150 C. for one hour. Filtration of this material yielded anoilsoluble liquid which showed the following:

Basic No. 8.9 Lithium percent" 0.37 Strontium do 1.27 Metal ratio 1.64

The remaining unfiltered product was treated with carbon dioxide for 90minutes at 150 C., then filtered. The filtrate was an oil-soluble,free-flowing liquid having the following analyses:

A phosphorusand sulfur-containing acid was prepared by treating apolyisobutylene with thiophosphoryl chloride, and then with steam. To amixture of 1074 grams (1.5 equivalents) of this acid and 992 grams ofmineral oil there was added portionwise 60 grams (1.5 equivalents) ofsodium hydroxide dissolved in 400 grams of water, and the salt mixtureheated for one hour at 50- 70 C. To this was added 186 grams (0.9equivalent) of diisobutyl phenol, and then at 5095 C. 451 grams (5.9equivalents) of barium oxide. This mixture was heated at refluxtemperature for one hour, then dried by heating up to 150 C.Approximately one third of this was dried further by continued heatingfor an hour at 150 C. Filtration of this sample yielded an oil-soluble,

non-viscous filtrate having the following analyses:

Basic No 17.9 Sodium ..percent 0.62 Barium do 11.05 Metal ratio 4.0

Basic No 0.6 Sodium percent 1.2 Barium do 12.1 Metal ratio 4.4

Example 18 To a mixture of 1220 grams (1.0 equivalent) of diei cosylsalicylic acid, grams (0.6 equivalent) of p-tertbutyl phenol, and 214grams of water there was added at 50 C. 42 grams (1.0 equivalent) oflithium hydroxide monohydrate. This mixture was heated at 50 C. for 15minutes, then treated with 301 grams (3.94 equiva lents) of barium oxideand heated at reflux temperature for one hour. The temperature wasraised to C. and a portion of the product was removed and dried at150-l60 C. for one hour, then filtered through a siliceous filter aid.This sample was found to have the following analyses:

Basic No 63.4

Lithium "percent" 0.22

Barium do 12.7

Metal ratio 3.9

Example 19 A mixture of 665 grams (1.0 equivalent) of a 60% oil solutionof sodium petroleum sulfonate, 20.6 grams (0.1 equivalent) of diisobutylphenol (ratio of equivalents of sulfonate to phenol is 10.0), 395 gramsof mineral oil and 132 grams of water was treated at 50 C. with 183grams (2.39 equivalents) of barium oxide, then heated at refluxtemperature for one hour. The resulting product was dried by heating to150 C. A sample 3 was withdrawn and dried further at 150 C. for onehour, then filtered. It was shown to have the following analyses:

Basic No 20.5 Sodium percent-.. 2.1 Barium do 8.3 Metal ratio 2.5

Example 20 Basic No 47.5 Sodium per 0.29 Barium do 6.4 Metal ratio 1.9

The remaining material was treated with carbon dioxide, then dried asabove and filtered. This material showed the following analyses BasicNo. 17.9 Lithium percent 0.22 Barium (10-....- 12.7 Metal ratio 4.

a The remainder was treated at 150' C. with carbon dioxide for one hourand heated at 150l60 C. for an additional hour. This material had thefollowing analyses Basic No. 5.93 Sodium percent..- 1 85 Barium d0 9.5Metal ratio 3.0

15 The thus-dried material was further treated with carbon dioxide forone hour at 150160 C., dried at this temperature for an additional hour,and filtered through a siliceous filter aid. The filtrate had thefollowing analyses:

Basic No 10.8 Sodium "percent" 0.25 Barium do 15.4 Metal ratio 4.6

Example 21 A mixture of 332 grams (0.5 equivalent) of a 60 percent oilsolution of sodium petroleum sulfonate, 315 grams (0.5 equivalent) ofpetroleum sulfonic acid, 753 grams of mineral-oil, and 135 grams ofwater was treated at 35-40 C. with 21 grams (0.5 equivalent) of lithiumhydroxide monohydrate. The temperature was raised to 80 C. and 124 grams(0.6 equivalent) of diisobutyl phenol was added: then at-87-92" C. 301grams (3.93 equivalents) of barium oxide was added portionwise over aperiod of 25 minutes. The resulting mixture was heated at refluxtemperature for one hour, then dehydrated by heating to 150 C. A samplewas removed, dried further by heating at 150-160 C. for an hour, thenfiltered through a siliceous filter aid. The filtrate was adark-,oil-soluble, viscous liquid, having the following analyses:

Basic No 64 Sodium percent 0.53 Lithium do 0.127 Barium d 11.3 Metalratio 3.84

The unfiltered portion of the product was treated further at 145-155 C.for one hour with carbon dioxide. A 30-minute period of heating at150155 C. followed and the product was filtered through a siliceousfilter aid.

The filtrate was an oil-soluble, free-flowing liquid having thefollowing analyses:

Basic No 3.3

Sodium percent 0.15

Lithium do 0.56

Barium ..do 13.2

Metal ratio 4.6

Example 22 To a mixture of 315 grams (0.5 equivalent) of petro- Basic No5.8 Potassium percent 2.53 Barium do 1.32 Metal ratio 1.60

The unfiltered portion of the product was treated with carbon dioxidefor an hour at 150155 C., then heated at this temperature for anadditional hour. The product was filtered through a filter aid yieldingan oil-soluble, free-flowing liquid having the following analyses:

Basic No 1.3 Potassium percent 1.89 Barium do.. 13.4 Metal ratio 4.67

Example 23 A mixture of 332 grams (0.5 equivalent) of a 60 percent oilsolution of sodium petroleum sulfonate, grams (0.3 equivalent) ofp-tert-butyl phenol and 633 grams of oil was treated at 70 C. with 260grams (1.96 equiva lents) of strontium hydroxide octahydrate, addedportionwise over a period of 20 minutes. This mixture was heated atrefiux temperature for an hour, then freed of water by heating to 150 C.A sample was withdrawn, dried by heating at 150l60 C. for an hour,

then filtered through a siliceous filter aid. The oilsoluble, slightlyviscous filtrate showed the following analyses:

Basic No 5.8 Sodium percent 1.16 Strontium do 0.17 Metal ratio 1.66

Basic No 1.3 Sodium percent 1.05 Strontium do 3.16 Metal ratio 2.74

Example 24 A product was prepared as in the preceding example, using asstarting materials sodium petroleum sulfonate, p-tert-butyl phenol andstrontium hydroxide octahydrate. After this product had been heated to150 C. it was treated with sulfur dioxide for an hour, then dried byheating at ll55 C. for another hour, and filtered. The filtrate was anoil-soluble, free-flowing liquid having the following analyses:

Basic No 3.3 Sodium ..percent 1.36 Strontium do 3.87 Metal ratio 2.82

Example 25 A mixture of 672 grams (1.0 equivalent) of a percent oilsolution of sodium petroleum sulfonate, 394 grams (1.0 equivalent) ofdi-Z-ethylhexyl dithiophosphoric acid, 40 grams (1.0 equivalent) ofsodium hydroxide, and 375 grams of water was warmed at 4050 C. for 20minutes, then treated at C. with 250 grams (1.25 equivalents) ofdiisobutylphenol, 680 grams (8.9 equivalents) of barium oxide, and 1622grams of mineral oil. This mixture was heated at reflux temperature forone hour, then freed of water by heating to C. A portion was removed,heated further at l40l60 C. for an hour, then filtered. The oil-soluble,free-flowing filtrate showed the following analyses:

Basic No 46.2 Sodium percent 1.27 Barium do 9.3 Metal ratio 3.25

The unfiltered portion of the product mixture was treated with carbondioxide for an hour at 150155 C., then after an additional 30-minuteperiod of heating at 150 C., it was filtered. The oil-soluble,non-viscous filtrate showed the following analyses:

Basic No 1.65 Sodium percent 1.20 Barium do 14.9 Metal ratio 4.46

Example 26 197 grams (4.92 equivalents) of sowas added 1500 grams (2.23equivalents) of white oil sulfonyl chloride and the mixture was heatedat reflux temperature for an hour. Water was removed by azeotropicdistillation with toluene and the dried-residue was filtered and thefiltrate diluted with 1510 grams of mineral oil and evaporated at 150C./ 20 mm. The residual sodium sulfonate was mixed with 390 grams (1.23equivalents) of cetyl phenol, 610 grams (7.97 equivalents) of bariumoxide and 325 grams of water and heated at reflux temperature for onehour, then freed of the water by heating to 150 C. A portion of thisproduct was heated for one hour at 150-160 C., then filtered; Theoil-soluble filtrate showed the following analyses:

Basic N 21.4 Sodium percent" 0.95 Barium o 5.65 Metal ratio 2.59

Basic No 2.7 Sodium percent 0.98 Barium d 11.3 Metal ratio 4.42

Example 27 A mixture of 600 grams (0.5 equivalent) of a 40 percent oilsolution of mixed'barium didodecylbenzene sulfonate and barium petroleumsulfonate (sulfateash content: 10.1%), 523 grams (0.5 equivalent) of a45 percent oil solutionof calcium petroleum sulfonate (sulfate ashcontent: 6.5%), 93 grams (0.6 equivalent) of o-chlorobenzamide, 135grams of water, and 654 grams of mineral 'oil was heated to 50 C. andtreated over a' 15-minute period with 165 grams (3.93 equivalents) oflithium hydroxide monohydrate. The mixture was heated at refluxtemperature for one hour, then freed of'water by heating to 150 C. Asmall sample was removed, dried further by heating at 150 C., andfiltered. The filtrate was an oil-soluble, free-flowing liquid, havingthe following analyses:

Basic N 4.95 Barium percent" 1.7 Calcium do 0.09 Lithium do 0.52 Metalratio 2.02

The unfiltered part of the product was treated at 145- 155 C. withcarbon dioxide for about an hour, dried by 30 minutes heating at 150 C.,and filtered. The oil-soluble, free-flowing filtrate showed thefollowing analyses:

Basic N 3.1 Barium percent 1.68 Calcium do 0.38 Lithium do 0.88 Metalratio 3.41

Example 28 18 was heated for one hour at reflux temperature, thendehydrated by heating to 150 C. A portion was removed, dried bycontinued heating at 150 C. for 30 minutes, and filtered. Theoil-soluble filtrate showed the follow- The unfiltered portion of theproduct was treated with carbon dioxide for an hour at 150 C., thendried by continued heating at 150 C. for 30 minutes, and filtered.

The filtrate was an oil-soluble, free-flowing liquid having thefollowing analyses:

Basic No. 2.36 Barium p cent... 12.5 Calcium do 0.12 Sodium do 0.60Metal ratio 4.30

Example 29 To a mixture of 315 grams of petroleum sulfonic acid (0.5equivalent) and 336 grams of mineral oil there was added a solution of33 grams (0.5 equivalent) of potassium hydroxide in 68 grams of water,and then 104 grams (0.5 equivalent) of tetralin sulfonic acid (ratio ofequivalents of sulfonic acid to promoter is 1.0). Finally, at 55-95 C.,151 grams (1.97 equivalents) of barium oxide was added portionwise overa period of 10 minutes, and the temperature was maintained thereafter at-105 C. for one hour. The temperature then was raised to C., 479 gramsof mineral oil added, and a portion of the resulting product removed anddried by heating for one hour at ISO-160 C. This sample was filtered,yielding an oil-soluble, free-flowing filtrate which show the followinganalyses:

Basic No. 5.4 Potassium p cent" 1.51 Barium do 5.47 Metal ratio 3.36

The balance of the unfiltered product was treated with carbon dioxide atC. for one hour, then filtered. The filtrate was oil-soluble and showedthe following analyses:

A mixture of 315 grams (0.5 equivalent) of petroleum sulfonic acid, 150grams of water and 283 grams of mineral oil was heated to 70 C.whereupon 21 grams (0.5 equivalent) of lithium hydroxide monohydrate wasadded and the mixture was heated at reflux temperature for an hour. Thetemperature was lowered to 70 C. and 171 grams (1.22 equivalents) ofstrontium hydroxide octahydrate, and 230 grams (2.44 equivalents) ofphenol were added. This mixture was heated at re- 19 Example 3] Amixture of 282 grams (1.0 equivalent) of oleic acid and 1119 grams ofmineral oil was treated at 90 C. with a solution of 42 grams (1.0equivalent) of lithium hydroxide monohydrate in 300 grams of water andthen heated at refiux temperature for one hour. To this mixture, at 80C., there was added 124 grams (0.6 equivalent) of diisobutylphenol and302 grams (3.94 equivalents) of barium oxide, and the Whole was heatedat reflux temperature for two hours. The mass was dehydrated by heatingto 150 C., then carbonated by treatment with carbon dioxide at thistemperature for about one hour. The resulting product was filteredyielding as a filtrate an oil-soluble, free-flowing liquid having thefollowing analyses:

The salt complexes produced in accordance with the present invention canbe employed in lubricants including oils and greases, and for suchpurposes as in crankcases, transmissions, gears, etc. as well as intorque converter oils. Other suitable uses for such complexes are inasphalt emulsions, insecticidal compositions, fire-proofing andstabilizing agents in plasticizers and plastics, paint driers, rustinhibiting compositions, pesticides, foaming compositions, cutting oils,metal-drawing compositions, flushing oils, textile treatmentcompositions, tanning assistants, metal cleaning compositions,emulsifying agents, antiseptic cleansing compositions, penetratingagents, gum solvent compositions, fat splitting agents, bonding agentfor ceramics and asbestos, asphalt improving agents, fiotation agents,improving agents for hydrocarbon fuels such as e. g., gasolene and fueloil, etc.

More particularly, the complexes of this invention are especiallyadapted for the preparation of lubricants, paint driers and plastics,particularly the halogen bearing plastics. In these respects, the saltcomplex can be employed in the following concentrations based upon theweight of the total composition.

Broad Usual Preferred Range, Range, Range,

Percent Percent Percent Lubricant 0. 01-20 0. 215 0. 5-10 StabilizingAgent or Plast 0. 05 5 0. 1- 3 0.2- 2 PaintDri zr.. 0.2- 0.5-20 1.0-15

I. Preparing and mixing a mass in which, at 50 C., at least 50% of thecomponents are in the liquid state, and in which mass the activecomponents consist of:

(i) at least one oil-soluble compound selected from the class consistingof:

(l) acidic organic compounds; (2) salts of acidic organic compounds; and(3) mixtures of (l) and (2) (ii) at least one compound other than thoseselected as component (1') selected from the class consisting of:

(1) compounds having the formula AH, in

which A is an anionic radical and H is hydrogen, which compounds:

(a) are water-soluble at a temperature of 50 C. to the extent of atleast .0005 and (b) in the presence of water, having an ionizationconstant greater than about 1X10 at about 25 C., the saturated aqueoussolutions of which at about 25 C. have pH values not greater than 7.0;

and which compounds are selected from the class consisting of:

(a') organic compounds and (b') inorganic compounds containing aplurality of atoms of an acid-forming element; and

(2) the metal salts of the compounds defined by (1) above;

the relative amounts of (i) and (ii) used being in the range of fromabout one equivalent of (i) to about ten equivalents of (ii) to aboutten equivalents of (i) to about one equivalent of (ii);

(iii) at least one compound other than those selected as components (i)and (ii) selected from the class consisting of:

(1) metal salts; and

(2) metal bases;

in an amount such that there are present in the mass a total ofsubstantially more than one equivalent of cationic salt-formingradicals, including those present in components (i) and (ii), perequivalent of (i) and (ii); and

(iv) at least one material selected from the class consisting of:

(1) water;

(2) the water-soluble alcohols and mixtures of such alcohols; and

(3) mixtures of water and such alcohols in an amount, inclusive of thatin chemical combination with all of the components present, equal to atleast one mole per mole of (iii); II. and then maintaining the mass at atemperature and for a period of time sufficient to drive offsubstantially all free water and alcohol, including water and alcohol ofhydration, which may be present, said process being characterizedfurther in that the metals present in the reaction mass include at leasttwo dissimilar metals selected from the class consisting of the metalsof Group I having an atomic weight of less than 40 and the metals ofGroup II having an atomic weight of less than 138, at least one of saidmetals is selected from group I, and at least one of said metals isselected from group II.

2. The process of claim 1 further characterized in that the process massis treated prior to filtering with an acidic material of which theionization constant is higher than the ionization constant of thecompounds of component (ii) and in amounts sufficient to liberate asubstantial proportion of said organic compound of component (ii).

3. The process of claim 1 further characterized in that the metalspresent in the reaction mass include barium and sodium.

4. The process of claim 1 further characterized in that the component(ii) is at least one phenol.

5. The process of claim 1 further characterized in that the component(ii) is at least one alkyl phenol.

6. The process of claim 1 further characterized in that the component(ii) is diisobutyl phenol.

7. The process of claim 1 further characterized in that component (i) isat least one sulphonic acid.

8. The process of claim 1 further characterized in that the process massis treated prior to filtering with CO2 in amounts sutficient to liberatea substantial proportion of said compound of component (ii).

21 9. The process of claim 1 further characterized in that component (i)comprises at least one alkyl aromatic sulphonic acid and at least onepetroleum sulphonic acid. 10. A product in accordance with the processof claim 1.

McLennan Mar. 18, 1947 10 22 McNab et a1. Apr. 15, 1947 Worth et a1. May6, 1952 Eckert Sept. 1, 1952 Asself et a1. Nov. 4, 1952 A-sself et al.Nov. 4, 1952 Asself et a1. Nov. 4, 1952 Asself et a1. Nov. 4, 1952Asself et a1. Nov. 4, 1952

1. A PROCESS WHICH COMPRISES: I. PREPARING AND MIXING A MASS IN WHICH,AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, ANDIN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: (I) AT LEAST ONEOIL-SOLUBLE COMPOUND SELECTED FROM THE CLASS CONSISTING OF: (1) ACIDICORGANIC COMPOUNDS; (2) SALTS OF ACIDIC ORGANIC COMPOUNDS; AND (3)MIXTURES OF (1) AND (2) (II) AT LEAST ONE COMPOUND OTHER THAN THOSESELECTED AS COMPONENT (I) SELECTED FROM THE CLASS CONSISTING OF: (1)COMPOUNDS HAVING THE FORMULA AH, IN WHICH A IS AN ANIONIC RADICAL AND HIS HYDROGEN, WHICH COMPOUNDS: (A) ARE WATER-SOLUBLE AT A TEMPERATURE OF50* C. TO THE EXTENT OF AT LEAST .0005 %; AND (B) IN THE PRESENCE OFWATER, HAVING AN IONIZATION CONSTANT GREATER THAN ABOUT 1X10-10 AT ABOUT25* C., THE SATURATED AQUEOUS SOLUTIONS OF WHICH AT ABOUT 25* C. HAVE PHVALUES NOT GREATER THAN 7.0; AND WHICH COMPOUNDS ARE SELECTED FROM THECLASS CONSISTING OF: (A'') ORGANIC COMPOUNDS AND (B'') IORGANICCOMPOUNDS CONTAINING A PLURALITY OF ATOMS OF AN ACID-FORMING ELEMENT;AND (2) THE METAL SALTS OF THE COMPOUNDS DEFINED BY (1) ABOVE; THERELATIVE AMOUNTS OF (I) AND (II) USED BEING IN THE RANGE OF FROM ABOUTONE EQUIVALENT OF (I) T ABOUT TEN EQUIVALENTS OF (II) TO ABOUT TENEQUIVALENTS OF (I) TO ABOUT ONE EQUIVALENT OF (II); (III) AT LEAST ONECOMPOUND OTHER THAN THOSE SELECTED AS COMPONENTS (I) AND (II) SELECTEDFROM THE CLASS CONSISTING OF: (1) METAL SALTS; AND (2) METAL BASES; INAN AMOUNT SUCH THAT THERE ARE PRESENT IN THE MASS A TOTAL OFSUBSTANTIALLY MORE THAN ONE EQUIVALENT OF CATIONIC SALT-FORMINGRADICALS, INCLUDING THOSE PRESENT IN COMPONENTS (I) AND (II), PEREQUIVALENT OF (I) AND (II); AND (IV) AT LEAST ONE MATERIAL SELECTED FROMTHE CLASS CONSISTING OF: (1) WATER; (2) THE WATER-SOLUBLE ALCOHOLS ANDMIXTURES OF SUCH ALCOHOLS; AND (3) MIXTURES OF WATER AND SUCH ALCOHOLSIN AN AMOUNT, INCLUSIVE OF THAT IN CHEMICAL COMBINATION WITH ALL OF THECOMPONENTS PRESENT, EQUAL TO AT LEAST ONE MOLE PER MOLE OF (III); II.AND THEN MAINTAINING THE MASS AT A TEMPERATURE AND FOR A PERIOD OF TIMESUFFICIENT TO DRIVE OFF SUBSTANTIALLY ALL FREE WATER AND ALCOHOL,INCLUDING WATER AND ALCOHOL OF HYDRATION, WHICH MAY BE PRESENT, SAIDPROCESS BEING CHARACTERIZED FURTHER IN THAT THE METALS PRESENT IN THEREACTION MASS INCLUDE AT LEAST TWO DISSIMILAR METALS SELECTED FROM THECLASS CONSISTING OF THE METALS OF GROUP I HAVING AN ATOMIC WEIGHT OFLESS THAN 40 AND THE METALS OF GROUP II HAVING AN ATOMIC WEIGHT OF LESSTHAN 138, AT LEAST ONE OF SAID METALS IS SELECTED FROM THE GROUP I, ANDAT LEAST ONE OF SAID METALS IS SELECTED FROM GROUP II.